Dehydrogenation of hydrocarbons



Patented Nov. 30, 1943 DEHYDROGENATION F HYDROCARBONS John F. Sturgeon, Chicago, Ill., assignor to Universal Oil Products Company, Chicago. 111., a

corporation of Delaware No Drawing. Application March 5, 1942, V

Serial No. 433,442

8Claims. (c1. 260 683) This is a continuation-in-part of my co-pending application Serial No. 293,923, filed September 8, 1939 which has matured into U. S. Patent 2,278,223.

This invention relates to the treatment of hydrocarbons to produce therefrom less-saturated hydrocarbons containing the same number of carbon atoms but a smaller number of hydrogen atoms per molecule. In a more specific sense, the invention is concerned with a process for dehydrogenating aliphatic hydrocarbons.

Paraffinio hydrocarbons, which are present in considerable amounts in natural gases, casinghead gases, cracked gases, etc., and which are frequently used only as fuel, are convertible into more useful unsaturated hydrocarbons by dehydrogenation in the presence of catalysts hereinafter set forth. Butenes and higher olefins are converted into diolefins, and normally liquid pa:- afiinic hydrocarbons are transformed into more useful olefinic and diolefinic products by catalytic dehydrogenation.

In one specific embodiment the present invention comprises a process for dehydrogenating ali= phatic hydrocarbons in the presence or" a catalyst formed by mixing hydrogels containing at least one component having a dehydrogenating catalytic activity in a partially dehydrated condition, filtering therefrom mechanically removable water, freezing and then thawing the hydrogel composite to destroy its gelatinous structure, filtering and washing the resultant material to remove water-soluble impurities, and drying, forming, and calcining to produce active catalyst.

In carrying out the dehydrogenation of various aliphatic hydrocarbons according to the present process, a solid composite catalyst in the form of particles of graded size or small pellets and prepared as hereinafter set forth, is used as a filter in reaction tubes, reactors, or chambers and the hydrocarbon to be dehydrogenated is passed through the catalyst after being heated to the proper temperature which is usually between about 750 and about 1409 F1, although more commonly between about 900 and about 1200 F. The catalyst reactors may also be heated exteriorly to maintain the proper temperature for the reaction which is carried out under a pressure which may be subatmospherio, atmospheric, or superatmospheric. While pressures up to approximately 506 pounds per square inch may be employed in some cases, pressures of atmospheric or below are frequently preferred. The time during which the hydrocarbons are exposed to dehydrogenating conditions in the presthrough which the vapors of the hydrocarbons are passed. Such operations may be conducted so that there is relatively little mechanical loss of catalyst from the reaction zone because of the carrying action of the reactant streams, or the rate of flow of vapors may be adjusted so that definite amounts of powdered catalyst are carried from the reaction zone and later separated from the treated vapors and reactivated by suitable treatment with an oxygen containing gas mixture.

In this specification and in the claims, the term aliphatic hydrocarbons is used in referring to alkanes, alkenes, and arylalkanes which are converted into more unsaturated hydrocarbons in the presence of the dehydrogenating catalysts herein described. Undenthe operating conditions also herein set forth the aliphatic hydrocarbons lose hydrogen from the carbon chain of the respective hydrocarbons, but do not lose hydrogen from a hydrocarbon ring or undergo appreciable cyclization to form an aromatic ring from a straight chain hydrocarbon. Under some circumstances the addition of steam to the hy drocarbon undergoing dehydrogenation, particularly in the case of hexane and higher hydrocarbons, is favorable to the production of olefinic.

hydrocarbons.

The time of contact employed will vary with the activity or" the catalyst used, the tempera; ture employed, and the hydrocarbon or hydrocarbon mixture undergoing treatment. The relatively low molecular Weight parafiins such as ethane and propane are generally more diflicult to dehydrogenate than the higher normally gaseous and liquid paraffins. Parafiinic hydrocarbons frequently require a higher catalyst temperature or longer time of contact than do the corresponding oleflns which are convertible into diolefinic hydrocarbons by dehydrogenation, said diolefin formation being carried out generally at a subatmospheric pressure. Production of 'arylalkenes by catalytic dehydrogenation of ethylbenzene or other alkylated aromatic hydrocarbons having at least one ethyl group or higher alkyl group, is preferably carried out at a relatively high temperatureby use of a short time of contact in the presence of the catalyst and under a reduced pressure in order to obtain drogels as herein set forth. The essential feature of the present invention is the use of catalyst composites containing an active dehydrogenating component prepared by freezing and thawing primarily composited hydrogels or hydrous oxides to eliminate water and then utilizing subsequent steps involving washing to remove impurities,-

forming. and calcining to produce formed particles or powdered catalyst of high dehydrogenating activity. I have found that the expedient of freezing and thawing to remove water and to facilitate washing of precipitated gelatinous materials is applicable to a wide range of materials of both a simpl and a complex character. Broadly speaking, I have found this method to be applicable to substantially all potentially catalytic materials which are capable of being precipitated in the form of a hydrogel or a hydrous oxide. The expedient of freezing and thawing is thus applicable to the hydrogels or hydrous oxides of the following elements: magnesium, zinc, and cadmium in the right-hand column of group II of the periodic table; aluminum in the right-hand column of group III; titanium, zirconium, cerium, and thorium in the left-hand column of group IV; silicon and tin in the righthand column of group IV; vanadium, columbium, and tantalum in the left-hand column of group V; chromium, molybdenum, and tungsten in the left-hand column of group VI; and iron, nickel, and cobalt constituting the fourth series of group VIII.

Since substantially all of the o..ides of'theseelements are alternatively utilizable in producing catalyst composites having dehydrogenating activities, it is readily seen that a considerable number of alternatively utilizable composite materials can be produced, although obviously the catalytic activities of the different possible composites will not be exactly equivalent particularly when dehydrogenating different hydrocarbons which may thus be converted into other hydrocarbons having the same number of carbon atoms but a smaller number of hydrogen atoms per molecule. Some of the oxides of these elements possess greater dehydrogenating activities than others, and some of the materials produced by the reduction of the oxides have greater activities than their oxides as is the case with iron, nickel, and cobalt. The oxides of chromium, molybdenum, tungsten, and vanadium all have outstanding activities in reactions involving the direct dehydrogenation of aliphatic hydrocarbons including particularly alkanes, alkenes, and arylalkanes, although in this group of oxides there are variations in activities with different hydrocarbons. The oxides of silicon,- titanium, zirconium, cerium, and thorium usually have lower dehydrogenating potency than those of chromium, molybdenum, tungsten, and vanadium and among themselves, cerium is usually highest in activity. The oxides of alua relatively high yield of desired product without times exhibit specific promoting eflects which are not exactly in accord with their individual activities in such reactions.

For producing dehydrogenation catalysts utilizable in the process of the present invention, hydrous oxides of most of the elements already mentione'd may be precipitated or hydrogels may be formed'by the addition of a basic precipitant to solutions of salts of the elements using for example ammonium hydroxide, ammonium carbonate, ammonium sulfide, or theireq'uivalents. For example, hydrogels of alumina and zirconia may be formed by the addition of ammonium hydroxide to solutions of aluminum and zirconium salts, or an alumina hydrogel may be produced by means of a solution of an aluminum salt reacting with an aqueous solution of an alkali metal aluminate. As further examples, vanadium pentoxide may be precipitated as an amorphous hydrous mass by the addition of a mineral acid to a concentrated solution of a vanadate of an alkali or alkaline earth metal, or hydrous vanadium sesquioxide may be precipitated by treating with ammonia an aqueous solution of vanadium trichloride. A precipitate of hydrated silica may be formed by acidifying an aqueous solution of an alkali metal silicate. These examples are mentioned only as instances of methods which may be employed primarily to form hydrous oxides but are not presented with the intention of limiting the scope of the invention to the use of the specific materials mentioned. Gels or hydrous oxides may be formed by any method found suitable or advantageous. Such gels may be formed separately, they'may be co-precipitated, or separately precipitated gels may be separately frozen and thawed and then mixed prior to final washing or prior to drying and washing in cases where it is advantageous to dry before removing water-soluble impurities by washing.

The solid powdered material obtained from the thawing of the hydrogel is dried preferably either at a moderate temperature not greatly in excess of about 212 F. or by the use of alcohol, acetone, or other water miscible solvent since heating alone at higher temperature frequently reconverts the wet powdered material into a hydrogel.

The exact conditions which are optimum for the freezing treatment of the gels, such as temperature and rate and time of freezing, are dependent upon the composition of the gel in question, its water content, and otherfactors: During freezing, the hydrogel composite loses its gel structure so that the thawing of the frozen material produces an aqueous solution and a fine powder-or granular material, the latter being readily and formed into particles by extrusion, pelleting,-

or other similar methods with or without the addition of promoters prior to the particle-forming operation. The pelleted, otherwise formed, or powdered catalytic material is then calcined at a temperature from about 900 to about 1500 F. to produce active catalyst.

The process of freezing precipitated hydrogel composites is applicable particularly to the preparation of dehydrogenation catalysts, such as alumina-chromia-magnesia, and may be used also in the preparation of any other catalyst which may be produced in the form of a precipitated hydrogel or hydrogel composite which requires washing to remove therefrom water-soluble impurities. Thus the freezing and thawing operations utilized in the production of the preferred dehydrogenating catalyst of the present invention may be applied to substantially any type of catalytic material which exists as a hydrogel during one phase of its manufacture and requires repeated washes with water and aqueous solutions to remove deleterious impurities.-

An advantage of utilizing freezing of hydrogel composites during the preparation of dehydrogenating catalysts is that the frozen and thawed catalytic composites may more easily be washed substantially free from alkali metal compounds than is possible when washing the original hydrogels. Furthermore, grinding of the frozen, thawed, purified and dried composite is frequently unnecessary before forming it into catalyst particles; and several drying and screening operations are avoided which must ordinarily be made when removal of impurities from precipitated hydrogel catalysts is effected mainly by washing. Also the apparent density of a catalyst prepared from a frozen hydrogel composite is less than that of a similar catalyst prepared from the same kinds of hydrogels which have not beenfrozen preparation of dehydrogenation catalyst composites to calcine them at a temperature between about 900 and about 1500" F. Such calcination treatment does not cause complete dehydration of the hydrated oxides, but gives catalytic materials of good structure and porosity so that they are able to resist for a long time the deteriorating effects of the service and reactivation period to which they are subjected.

The dehydrogenating value of different composites and the activity of composites having different proportions of oxide ingredients have been found to vary considerably with the methods of preparation of the composites. alumina-chromia-magnesia catalysts the most effective and economical proportions comprise major amounts of alumina and relatively minor amounts of chromia and magnesia; while in other cases best results are obtained when employing catalysts containing major amounts of catalyst components having relatively ,high dehydrogenating activities and minor amounts of oxides having relatively low catalytic activities such as alumina, magnesia, 'zinc oxide, and cadmium oxide.

In preparing dehydrogenation catalysts of the alumina-chromia-magnesia type, alumina and chromia may be composited and mixed with relatively minor amounts of magnesia in several ways to form composites which may be calcined at a temperature between about 900 and about 1500 F. to produce active dehydrogenating catalysts.

According to one method of preparation a precipitated alumina hydrogel is prepared by addition of a base to an aluminum salt, as the chloride, nitrate, or sulfate, or precipitated alumina hydrogel is formed by the addition of an acid such as hydrochloric or sulfuric, or of a solution of an aluminum salt, to a sodium aluminate solution. Alumina hydrogel so formed is frozen In the case of' and then thawed so as to break down the gel structure producing hydrated aluminum oxide in powdered form, which is separated from mechanically removable water, washed to remove watersoluble impurities, and dried. It is preferable to precede the washing step by drying treatments.

The finally dried powder is then impregnated with a solution of chromic acid dissolved in water, and the desired quantity of magnesium oxide is then added to the impregnated powder. The resultant composite of hydrous aluminum oxide and compounds of chromium and magnesium is then dried and calcined; or dried, formed in particles, and calcined.

According to a second method, hydrated aluminum oxide is prepared by precipitation, and the hydrogel is'frozen, washed, and dried as in the first method. Then the hydrated aluminum oxide is activated by being calcined at a tem-' perature between about 900- and about 1500 F. to produce activated alumina which is impregnated with chromic acid solution and the desired amount of magnesium hydroxide is added thereto. By a third method of preparation, aluminum and chromium salts, such asthe nitrates, are

dissolved in water and alumina and chromia hydrogels are coprecipitated therefrom by addition of a base, such as ammonium hydroxide, ammonium carbonate, or other suitable precipitant. The resultant hydrogel composite is frozen, thawed, filtered, washed, and-dried,'and the desired proportion of magnesium hydroxide is then added to the dried alumina-chromia composite after which the resultant mixture is next formed into particles and calcined to produce an active dehydrogenation catalyst. Instead of adding magnesium hydroxide to the alumina-chromia composite it is also possible to effect substantially the same improvement in the final catalyst by similarly adding magnesium chromate. Also, alumina, chromia, and magnesia hydrogels formed separately by precipitation may be admixed to produce the desired composite catalyst.

Variable factors will be introduced in the preparation of the present types of catalysts when different methods of mechanical mixing, wet precipitation, co-precipitation, and calcination are used and variable results will be obtained also, depending upon the character of the particles employed in the dehydrogenation operations; that is, whether they are used as powder, granules, or in the form of pellets or extruded particles.

Since the usual method of operating commercial dehydrogenation plants. is to utilize several catalyst reactors, each containing at least one fixed catalyst bed, connected in parallel so that one reactor may be utilized in dehydrogenating a hydrocarbon charge while the other is being reactivated, as by heating in an oxygen-containing gas, it is preferable to so balance conditions in the two parts of the cycle that the times of processing and reactivation are substantially equal. A further problem to be solved by trial is the question of the length of the operating cycle, since best overall results are usually obtained in continuous plants when operations are conducted for relatively short intervals followed by a correspondingly short time of reactivation rather than by allowing the catalyst particles to become contaminated excessively by carbonaceous deposits.

Products from the catalytic reactors are subjected to suitable treatment to remove therefromthe hydrocarbons formed by dehydrogenation,

while the unconverted hydrocarbon material is recycled to furtherv contact with the catalyst;

For example, olefinic or diolefinic materials resulting from dehydrogenation of parafllns, olefins, or alkylated aromatic hydrocarbons may be sirable and commercially valuable derivatives. After the most reactiveproducts have been removed,' the residual materials are then recycled for further treatment with or without comple removal of hydrogen.

Many of the composites included in the present types of catalysts are selective in removing two hydrogen atoms from a parafiinmolecule to produce the corresponding olefin without furthering to any great extent undesirable sid reactions, and because of this, there is an unusually high conversion of paraflins into olefins, as will be shown in the example. When the activity of such a catalyst begins to diminish,'it is readily reactivated by the expedient of oxidizing with air or other oxidizing gas at a moderately elevated temperature, usually within the range employed in thedehydrogenating reactions. This oxidation efiectively removes most of the carbonaceous deposits which gradually contaminate the surface of the particles during the processing period and decrease their efllciency. It is characteristic of such catalysts that they may be reactivated repeatedly without substantial loss of catalytic efficiency.

' When reactivating partly spent catalysts by oxidation with air or other oxidizing gas mixtures, lower metal oxides are sometimes oxidized to higher oxides which may combine to a greater or lesser extent with some of the other components in the catalyst mixture to fonn salts. For example, the oxide CraOa is extensively oxidized to CIO3 during reactivation of the spent aluminachromia catalyst with an oxidizing gas mixture and the chromium trioxide combines with'alumina toform a chromate. Later, this chromate. or the adsorption complex of Cr03 on A1203 is apparently decomposed by contact with reducing gases in the first stages of service to reform the green sesquioxide CrzOa, and regenerate the real catalyst and hence the catalytic activity.

In the dehydrogenation of butanes it has been found essential that particular conditions of operation be observed in order to produce maximum yields of butenes in the presence of aluminum oxide-chromium sesquioxide catalysts of suitable activity. In regard to temperature, the optimum range is from about 1000 to about 1200 F., at the surface of the catalytic particles. It is essential, in combination with a suitable hourly space velocity (volumes of butane charged per hour per volume of gross catalyst space), that this temperature be maintained within this relatively narrow range and that it be measured in the catalyst mass at a suflicient number of points so. that the average temperature falls within this interval. It is customary in many commercial plants to measure inlet and outlet temperatures of catalyst chambers and townsider the average temperature to be the mean of these two. But this is not accurate practice, since dehydrogenation reactions are endothermic and the average temperature would not be represented by the mean of the inlet and outlet on account of the need for adding heat externally.-

In using the above conditions of temperature,

5 the surface of the catalyst and a minimum of side reactions, such as would result in the formation of degradation products resulting from the scission of the carbon-to-carbon bonds. If a time' of contact is maintained corresponding to a maximum once-through yield 'of butenes (which may be as high as 50 to 60%) the deposition of carbon is greatly accelerated and demethanization and other splitting reactions rather than dehydrogenation occur, whereas when approximately a 25% conversion per pass is maintained it is possible to produce ultimate yields of approximately 95% of butenes by recycling of unconverted butane. Further, it has been determined that in dehydrogenation of hutanes by the preferred catalysts, the rate of carbon deposition passes through a minimum. within the temperature range given. That is, if temperatures lower than about 1100 F. are employed and the time of contact is increased to obtain approximately 25% conversion per pass,

a relatively large amount of carbon is'deposited and similarly the rate of carbon deposition begins to rise markedly at temperatures above about 1290 F. even though the time of contact is reduced to maintain only a 25% conversion per pass.

The following example is submitted to show specific results obtained in dehydrogenating butane in the presence of catalysts prepared by methods involving the freezing and thawing of hydrogel composites, although the data submitted are not intended to limit correspondingly the generally broad scope of the invention.

Three comparative dehydrogenation catalysts 40 were prepared so as to have compositions corresponding to the molecular ratios of 30Al203 I 3CI203 I 2MgO One of these composites was prepared by the 5 usual method of the prior art comprising precipitating aluminum hydroxide from aluminum sulfate solution by the addition of aqueous ammonia, repeatedly washing to remove Water-soluble impurities, and drying to produce aluminum oxide powder which was impregnated with aqueous chromic acid solution to which precipitated magnesium hydroxide had been added previously. The other two composites were prepared by methods described in this specification involving freezing and thawing of a precipitated alumina hydrogel to break up its gelatinous structure and "form powdered material which was washed more easily than thegelatinous hydrogel to remove water-soluble impurities. In the preparation of the second of these active catalysts, the alumina was activated by heating the washed material to 950 F. prior to 'compositing with chromia and magnesia.

Each of these three catalyst composites was dried, formed into 3x3 mm. cylindrical particles was passed at 1112 F. under atmospheric pressure using an hourly gaseous space velocity of 1500 and a dehydrogenating period with a duration of 45 minutes. The commercial butane fraction charged contained 4.3 mole per cent propane, 54.0% isobutane, 40.9% normal butane,

TABLE Dehydrogenation of a butane fraction in the presence of alumina-chromia-magnesia catalysts Catalysts prepared by- Precipitat- Precipltat- Precipitating, freezing, washlug, ireecing, washing, o oming, washing, activatpositmg, ing, coming, comand positing and positing, calcining calcining and calcining Oleflns produced per pass,

volume per cent:

thylene 1.0 0.3 Propy 1. 1 Butylenes 22. 2 28. 9 25. ll Total 23.2 29. 8 9

From the results given in the table, it is evident that dehydrogenation catalysts prepared from from mechanically removable water, freezing and then thawing the hydrogel composite to destroy its gelatinous structure, filtering, drying, and washing the resultant material to remove water-soluble impurities, drying, forming into particles, and calcining to produce active catalyst. 4. A process for dehydrogenating aliphatic hydrocarbons which comprises subjecting an aliphatic hydrocarbon at a temperature of from about 750 F. to about 1400" F. to contact with a catalyst prepared by mixing hydrogels contain ing at least one component having dehydrogenating activity in a partially dehydrated condition, filtering therefrom mechanically. removable water, freezing and then thawing the hydrogel composite to destroy its gelatinous structure,

I filtering, purifying, drying, forming, and calcining the resultant material to produceactive precipitated hydrogels which have been frozen to break down the gelatinous structure of the hydrogels are superior in dehydrogenating activities to a dehydrogenation catalyst of like composition prepared by the more-tedious method of the prior art necessary when freezing and thawing are not utilized in the catalyst preparation procedure.

The character of the present invention and its novelty and utility can be seen from the preceding specification and numerical data presented,

. although neither section is intended to unduly limit its generally broad scope.

I claim as my invention:

1. A process for "dehydrogenating aliphatic hydrocarbons which comprises subjecting an aliphatic hydrocarbon under dehydrogenating conditions to contact with a catalyst prepared by mixing hydrogels containing at least one component having dehydrogenating activity in a partially dehydrated condition, filtering therecatalyst.

5. A process for dehydrogenating paramnic hydrocarbons I which comprises subjecting a pure hydrocarbon at a temperature of from. about 750 F. to about 1400 F. to contact with a catalyst prepared by mixing hydrogels containing at least one component having dehydrogenating activity in a partially dehydrated condition, filtering therefrom mechanically removable water, freezing and then thawing the hydrogel composite to destroy its gelatinous structure, filtering, purifying, drying.'i'0rmlng, and calcining the resultant material to produce active catalyst.

6. A process for dehydrogenating olefinlc hydrocarbons which comprises subjecting an olefinic hydrocarbon at a temperature of from about 750 F. to about 1400 F. to contact with a catalyst from mechanically removable water, freezing and a then thawing the hydrogel composite to destroy its gelatinous structure, filtering. Purifying, dryprepared by mixing hydrogels containing at least one component having denydrogenating activity in a partially dehydrated condition, filtering therefrom mechanically removable water, freezing and then thawing the hydrogel composite to destroy its gelatinous structure, filtering. purifying, drying, forming, and calcining the resultant material to produce active catalyst.

7. A process for dehydrogenating arylalkane hydrocarbons which comprises subjecting an arylalkane hydrocarbon at a temperature of from about 750 F. to about 1400 F. to contact with a catalyst prepared by mixing hydrogels containing at least one component having dehydrogenating'activity in a partially dehydrated condition,

from mechanically removable water, freezing and then thawing the hydrogel compositeto destroy its gelatinous structure, filtering and washing the resultant material to remove watersoluble impurities, drying, and calcining the filtering therefrom mechanically removable water, freezing and then thawing the hydrogel composite to destroy its gelatinous structure,

filtering, purifying, drying, forming, and calcln ing the resultant material to produce active catalyst.

8. A process for dehydrogenating aliphatic hydrocarbons which comprises subjecting an allphatic hydrocarbon and a relatively minor proportion of steam to contact at a temperature of from about 750 F. to about 1400 F. in the presence of a catalyst prepared by mixing hydrogels containing at least one component having dehydrogenating activity in a partially dehydrated condition, filtering from mechanically removable water, freezing and then thawing the hydrogel composite to destroy its gelatinous structure, filtering. Purifying, drying, forming, and calcining the resultant material to produce active catalyst.

JOHN F. STURGEON. 

